超支化乙二胺三嗪聚合物对PPC/PBS共混体系的增强改性研究

以超支化乙二胺三嗪聚合物（HBETP）为改性剂,采用熔融共混法制备了聚碳酸亚丙酯（PPC）/聚丁二酸丁二醇酯（PBS）/HBETP共混物;利用动态热机械分析仪、热失重分析仪、电子万能试验机、旋转流变仪、扫描电子显微镜等,对其热性能、力学性能、流变性能、断面形貌等进行了表征。结果表明,当HBETP含量为0.5 %（质量分数,下同） 时,PPC/PBS/HBETP共混物在韧性基本保持不变的情况下,拉伸强度提高幅度最大,由7.56 MPa提高到11.22 MPa,增幅为49.6 %;HBETP的加入可以提高PPC/PBS的相容性,且适当的含量会使PPC/PBS的拉伸强度提升。     

Heat Resistant and Mechanical Properties of Biodegradable Poly(Lactic Acid)/Poly(Butylene Succinate) Blends Crosslinked by Polyaryl Polymethylene Isocyanate

This work focus on improving the heat resistant and mechanical properties of poly(lactic acid)/poly(butylene succinate) (PLA/PBS) blends using appropriate contents of polyaryl polymethylene isocyanate (PAPI). Some crosslinked structures were formed according to the gel fraction and rheological results, and the crosslinked structures played the role of nucleation site for the blends. And the Vicat softening temperature of the blends gradually increased with increasing PAPI content. Moreover, the addition of PAPI in the PLA/PBS blends produced a few PLA-PBS copolymers which acted as a compatibilizer and enhanced the interfacial adhesion. Thus, the mechanical properties of PLA were significantly improved.     

Immiscible PHB/PBS and PHB/PBSA blends: morphology,phase composition and modelling of elastic modulus

This paper reports the thermal, morphological and mechanical properties of environmentally friendly poly(3-hydroxybutyrate) (PHB)/poly(butylene succinate) (PBS) and PHB/poly[(butylene succinate)-co-(butylene adipate)] (PBSA) blends, prepared by melt mixing. The blends are known to be immiscible, as also confirmed by the thermodynamic analysis here presented. A detailed quantification of the crystalline and amorphous fractions was performed, in order to interpret the mechanical properties of the blends. As expected, the ductility increased with increasing PBS or PBSA amount, but in parallel the decrease in the elastic modulus appeared limited. Surprisingly, the elastic modulus was found properly described by the rule of mixtures in the whole composition range, thus attesting mechanical compatibility between the two blend components. This unusual behavior has been explained as due to co-continuous morphology, present in a wide composition range, but also at the same time as the result of shrinkage occurring during sequential crystallization of the two components, which can lead to physical adhesion between matrix and dispersed phase. For the first time, the elastic moduli of the crystalline and mobile amorphous fractions of PBS and PBSA and of the mobile amorphous fraction of PHB at ambient temperature have been estimated through a mechanical modelling approach. © 2021 The Authors. Polymer International published by John Wiley & Sons Ltd on behalf of Society of Industrial Chemistry.     

Crystallization behavior of partially crosslinked poly(β‐hydroxyalkonates)/poly(butylene succinate) blends

Partially crosslinked poly(β‐hydroxybutyrate‐co‐β‐hydroxyvalerate)/poly(butylene succinate) (PHBV/PBS) and poly(β‐hydroxybutyrate)/poly(butylene succinate) (PHB/PBS) blends were prepared by melt compounding with dicumyl peroxide. The effect of partial crosslinking on crystallization of the PHBV/PBS and PHB/PBS blends was investigated systematically. Differential scanning calorimetry results showed that the overall crystallization rates of both PHBV and PBS in their blends were enhanced considerably by the partial crosslinking. Similar results were also detected in the PHB/PBS blends. The polarized optical microscope observation displayed that the nuclei density of PHBV was increased while the spherulitic morphology did not change much. Conversely, the PBS spherulites turned into cloud‐like morphology after the partial crosslinking which is a result of the decrease in spherulite size, the reduction in interspherulite distance and the interconnection of fine PBS domains. Wide angle X‐ray diffraction patterns confirmed the enhancement in crystallization of the PHBV/PBS blends after the partial crosslinking without modification on crystalline forms of the PHBV and PBS components. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41020.     

Mechanical properties, morphology, and crystallization behavior of blends of poly(l-lactide) with poly(butylene succinate-co-l-lactate) and poly(butylene succinate)

The blends of poly(l-lactide) (PLLA) with poly(butylene succinate) (PBS) and poly(butylene succinate-co-l-lactate) (PBSL) containing the lactate unit of ca. 3 mol% were prepared by melt-mixing and subsequent injection molding, and their mechanical properties, morphology, and crystallization behavior have been compared. Dynamic viscoelasticity and SEM measurements of the blends revealed that the extent of the compatibility of PBSL and PBS with PLLA is almost the same, and that the PBSL and PBS components in the blends with a low content of PBSL or PBS (5-20 wt%) are homogenously dispersed as 0.1−0.4 μm particles. The tensile strength and modulus of the blends approximately followed the rule of mixtures over the whole composition range except that those of PLLA/PBS 99/1 blend were exceptionally higher than those of pure PLLA. All the blends showed considerably higher elongation at break than pure PLLA, PBSL, and PBS. Differential scanning calorimetric analysis of the blends revealed that the isothermal and non-isothermal crystallization of the PLLA component is promoted by the addition of a small amount of PBSL, while the addition of PBS was much less effective.     

Eco-friendly cellulose acetate butyrate/poly(butylene succinate) blends: crystallization,miscibility, thermostability,rheological and mechanical properties

In this work, the crystallization, miscibility, thermostability, rheological and mechanical properties of cellulose acetate butyrate (CAB)/poly(butylene succinate) (PBS) blends were investigated in detail. Differential scanning calorimetry analysis confirmed that PBS could form crystalline phase in the solution casted CAB/PBS blends with W_CAB?≤?60 wt.%. When the blends were crystallized from melt, the crystallization of PBS was found to be severely suppressed by the amorphous diluent of CAB. CAB and PBS were confirmed to be thermodynamic miscible in molten state by the negative value of Flory-Huggins interaction parameter (χ₁₂?=??0.89) between CAB and PBS. The rheological characterization results and thermogravimetric analysis revealed that the melt viscosity and thermostability of CAB were reduced and improved by blending CAB with PBS, respectively. Moreover, the rigid CAB became more flexible after incorporating with ductile PBS. The application of CAB is expected to be extended via blending the two species of eco-friendly polymers.     

Fabrication and characterisation of thermoplastic starch/poly(butylene succinate) blends with maleated poly(butylene succinate) as compatibiliser

Thermoplastic starch/poly(butylene succinate) (TPS/PBS), an entirely biodegradable polymer blend, was prepared by a two-step extrusion method. Maleic anhydride grafted PBS (rPBS) was successfully synthesised as an interfacial compatibiliser. The miscibility, morphology, thermal behaviour and mechanical properties of the TPS/PBS blends were investigated. The results demonstrated that the strength and elongation at break of TPS/PBS blends were greatly increased with the addition of rPBS in PBS blends due to improved interfacial miscibility. Better distribution and smaller phase domain were observed in the blends with higher content of compatibilisers. The water resistance was also enhanced by incorporation of rPBS. It was indicated that compatibilised TPS/PBS blends possessed a combination of good biodegradability, improved strength and high water resistance. TPS/PBS blend was expected to serve as a promising packing material.     

Morphology,rheology, crystallization behavior,and mechanical properties of poly(lactic acid)/poly(butylene succinate)/dicumyl peroxide reactive blends

The reactive blends were prepared by the blending of poly(lactic acid) (PLA) with poly(butylene succinate) (PBS) in the presence of dicumyl peroxide (DCP) as a radical initiator in the melt state. The gel fractions, morphologies, crystallization behaviors, and rheological and mechanical properties of the reactive blends were investigated. Some crosslinked/branched structures were formed according to the rheological measurement and gel fraction results, and the crosslinked/branched structures played the role of nucleation site for the reactive blends. The PLA–PBS copolymers of the reactive blends acted as a compatibilizer for the PLA and PBS phases and, hence, improved the compatibility between the two components. Moreover, it was found that the reactive blends showed the most excellent mechanical properties as the DCP contents were 0.2 and 0.3 phr. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39580.     

PHBV/PBS共混物的性能研究

通过熔融共混的方法制备了聚β-羟基丁酸戊酸酯/聚丁二酸丁二醇酯(PHBV/PBS)共混材料。研究了PHBV/PBS共混物的力学性能、相形态、结晶性能、热性能及晶胞结构。结果表明,将PHBV和PBS共混后,PHBV的韧性会有明显改善。当PHBV/PBS/TEC质量比为20/80/5时,PHBV的断裂伸长率由原来的5.7%增至124%、冲击强度由1.7 kJ/m2增加到4.3 kJ/m2,分别为PHBV的21.7倍和2.5倍。DSC研究表明,PBS的加入抑制了PHBV的结晶,但当PHBV/PBS/TEC质量比为20/80/5时,共混物出现了共晶现象。XRD显示PBS的加入在一定程度上影响了PHBV的晶型,复合材料的晶面特征峰发生了明显偏移。     

表面改性CNF对PBS/PLA共混物的湿热老化行为的影响

以硅烷偶联剂KH550对纳米纤维素(CNF)进行表面改性,利用双螺杆挤出机熔融共混制备一系列聚丁二酸丁二醇脂(PBS)/CNF母粒改性聚乳酸(PLA)复合材料,并在湿热老化试验箱中进行老化试验。通过扫描电子显微镜、广角X射线衍射仪、差示扫描量热仪、偏光显微镜等对复合材料的结晶和力学性能进行测试。结果表明,CNF可作为异相成核剂改善PLA的结晶行为,使PLA的结晶度提高;改性后,PBS/CNF复合母粒与PLA基体之间的相容性有较大改善;老化36 h后,PLA/PBS/CNF-KH550复合材料结晶进一步完善,其结晶度、拉伸强度和断裂伸长率较老化前分别提高了28.15 %、5.54 %和8.23 %。     

Preparation of PBT/POE-g-GMA/PP ternary blends with good rigidity–toughness balance by core–shell particles

Compared with poly(butylene terephthalate)/glycidyl methacrylate grafted poly(ethylene–octene) (PBT/POE-g-GMA) binary blends, supertough PBT-based ternary blends with little rigidity loss were successfully obtained by adding rigid polypropylene (PP) into PBT/POE-g-GMA blends to construct core–shell particles during melt blending. The effects of PP content and type on the phase morphology and mechanical properties of the blends were systematically investigated. Theoretical predictions and scanning electron microscopy observation showed that a core–shell structure was formed in PBT matrix with PP as the core and POE-g-GMA as the shell. The mechanical property tests showed that POE-g-GMA and PP had significant synergistic toughening effect. When PP with high melt flow index (H-PP) was used, PBT/POE-g-GMA/H-PP (70/15/15) blends possessed the highest Izod notched impact strength, which was 1.9-fold compared with PBT/POE-g-GMA (70/30) binary blends, while the tensile performance loss was little. The essential work of fracture tests was performed to evaluate the fracture resistance of different samples. The results demonstrated that PBT/POE-g-GMA/PP ternary blends possessed much better resistance to crack propagation than PBT/POE-g-GMA binary blends. The decrease of interparticle distance and the fibrillation of core–shell particles activated intense matrix shear yielding, which was the reason for the high crack resistance of ternary blends. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48872.     

Reactive compatibilization of poly(l‐lactide)/poly(butylene succinate) blends through polyester maleation: from materials to properties

The melt blending of poly(l ‐lactide) (PLLA) with biodegradable poly(butylene succinate) (PBS) is considered with a view to fine‐tuning its mechanical properties and its degradability. For this purpose, both maleic‐anhydride‐grafted PLLA (PLLA‐g‐MA) and maleic‐anhydride‐grafted PBS (PBS‐g‐MA) were prepared and used as reactive compatibilizers. The influence of PBS melt viscosity on the morphology and mechanical properties of PLLA/PBS blends was studied. Interestingly, the blending of low viscosity PBS with PLLA allows PLLA to be toughened while the use of high viscosity PBS led to PLLA/PBS blends exhibiting co‐continuous morphology. The nanostructure of the co‐continuous blends may be tuned through the joint action of organo‐modified clays and reactive compatibilizers. The effect of PBS on PLLA degradability was also investigated. The accelerated weathering testing of blends reveals that such combination of biodegradable polymers allows their degradability rate to be tailored. It is found that the addition of 20 wt% PBS to PLLA allows the molar mass loss fraction to be doubled after 425 h of testing. © 2014 Society of Chemical Industry     

PLA/PBS共混物增黏改性的研究

采用熔融反应共混法,通过引入过氧化二苯甲酰(BPO),对聚乳酸/聚丁二酸丁二醇酯(PLA/PBS)进行增黏改性。研究了该PLA/PBS反应共混物的流变性能、凝胶分数、热性能、力学性能和断面微观形貌。结果表明:随着BPO用量的增加,PLA/PBS反应共混物的转矩和凝胶分数均增大;PLA/PBS反应共混物的结晶性和熔点(Tm)随着BPO用量的增加而降低,且出现熔融双峰,当BPO用量增至1 phr时,熔融双峰消失,PLA和PBS间的相容性显著改善;随着BPO用量的增加,PLA/PBS反应共混物的断裂伸长率、拉伸强度、冲击强度均有所提高,而玻璃化转变温度(Tg)先降后升,体系的内耗则逐渐降低。     

Evaluation of mechanical properties of polypropylene/polycarbonate/SEBS ternary polymer blends using Taguchi experimental analysis

In this work, ternary polymer blends based on polypropylene (PP)/polycarbonate (PC)/poly(styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene) (SEBS) triblock copolymer and a reactive maleic anhydride grafted SEBS (SEBS‐g‐MAH) at fixed compositions are prepared using twin‐screw extruder at different levels of die temperature (235‐245‐255°C), screw speed (70‐100‐130 rpm), and blending sequence (M1‐M2‐M3). In M₁ procedure, all of the components are dry blended and extruded simultaneously using Brabender twin‐screw extruder, whereas in M₂ procedure, PC, SEBS, and SEBS‐g‐MAH minor phases are first preblended in twin‐screw extruder and after granulating are added to PP continuous phase in twin‐screw extruder. Consequently, in M₃ procedure, PP and SEBS‐g‐MAH are first preblended and then are extruded with other components. The influence of these parameters as processing conditions on mechanical properties of PP/PC/SEBS ternary blends is investigated using L9 Taguchi experimental design. The responding variables are impact strength and tensile properties (Young's modulus and yield stress), which are influenced by the morphology of ternary blend, and the results are used to perform the analysis of mean effect as well. It is shown that the resulted morphology, tensile properties, and impact strength are influenced by extrusion variables. Additionally, the optimum processing conditions of ternary PP/PC/SEBS blends were achieved via Taguchi analysis. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Fractionated crystallization, polymorphic crystalline structure, and spherulite morphology of poly(butylene adipate) in its miscible blend with poly(butylene succinate)

It has been investigated the effects of poly(butylene succinate) (PBS) component on the fractionated crystallization, crystalline structure, and spherulite morphology of polymorphic poly(butylene adipate) (PBA) with melting temperature lower than that of PBS in their miscible binary blends. Fractionated crystallization of the PBA component occurs upon blending with PBS depending on the content and crystallization temperature of the PBS component. It is probably related to the distribution of PBA in the PBS matrix. The PBS component suppresses the crystallization of PBA, due to the physical confinement effect of PBS on the PBA component. PBS is favorable for the formation of the PBA α-crystal in the PBS/PBA blends with C_PBS ≤ 70%, suggesting that the polymorphism of PBA can be regulated by PBS. The morphology observation reveals that the spherulite growth direction of PBA is controlled by that of PBS. Furthermore, the morphology of PBA is also manipulated by that of PBS rather than the crystallization temperature. The possible mechanism of morphology generation of PBA controlled by PBS has been proposed. The PBS/PBA blend system is an ideal system to study not only on the polymorphism regulation but also on morphology control of biodegradable polymorphic material by polymer blending without losing the biodegradability.     

Morphology evolution of poly(lactic acid) during in situ reaction with poly(butylenesuccinate) and ethylene-methyl acrylate-glycidyl methacrylate: The formation of a novel 3D star-like structure

Morphology control of polymer alloys is an attractive topic for investigators due to its ability to improve the performance of products for years. However, it is hard to control the morphology of immiscible polymer blends during melt processing. Herein, we studied the morphology evolution of poly(lactic acid) (PLA)/poly(butylene succinate) (PBS) with the inclusion of ethylene-methyl acrylate-glycidyl methacrylate (EGMA). Scanning electron microscopy of both cryo-fractured and etched cryo-fractured samples indicates that the in situ reaction among PLA, PBS, and EGMA can induce the morphology change and result in a novel 3D star-like structure. Rheology behaviors of the samples under different angular frequencies were used to validate the formation of 3D networks in the samples. Tensile stiffness reinforcements at both room temperature and high temperature were provided through dynamic mechanical analysis. In addition, a 10-fold improvement in impact strength is also monitored by the unnotched impact test to indicate the superior toughening effect. Furthermore, the crystalline behavior and thermal properties of the blends were also studied. It is believed that our work not only gives a deeper understanding of the reaction-induced morphology evolution of the PLA/PBS/EGMA blends but also reveals an avenue toward morphology control by melt processing.     

Morphology and hydrogen‐bond restricted crystallization of poly(butylene succinate)/cellulose diacetate blends

Poly(butylene succinate)/cellulose diacetate (PBS/CDA) blends were prepared by the solution blending method from poly(butylene succinate) (PBS) and cellulose diacetate (CDA). The influence of hydrogen bond on the structure, morphology, crystallization, as well as the physical properties of PBS/CDA blends was significantly investigated. The fourier transform infrared spectroscopy (FTIR) results indicated that the carbonyl groups of PBS shifted to higher wavenumbers and disappeared at the content of 60% CDA, due to the formation of hydrogen bond between PBS and CDA. The wide‐angle X‐ray diffractometer (WAXD) and differential scanning calorimeter (DSC) analysis suggest that the crystallization of PBS was significantly restricted by the incorporation of CDA, which is also attributed to the hydrogen bonding. The scanning electron miscroscope (SEM) and polarized optical microscopy (POM) results revealed that PBS and CDA were miscible without appearance of obvious phase separation. The hydrogen bonding interaction led to the change of decomposing mechanism of blends as determined by thermogravimetric analysis (TGA), as well as the increase of the elongation at break due to the reduced crystallinity of PBS. The existence of CDA led to the decrease of water contact angle, showing of the improved hydrophilicity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Blending Modification of PHBV/PBS/PEG and its Biodegradation

This study used poly(butylene succinate) and poly(ethylene glycol) to modify poly(3-hydroxybutyrate-co-3-hydroxyvalerate). The results showed that the incorporation of poly(butylene succinate) and poly(ethylene glycol) improved the mechanical properties of blends. The results showed that crystallinity of the poly(ethylene glycol)-containing blends decreased, so do the crystallization temperature and melting temperature of the poly(3-hydroxybutyrate-co-3-hydroxyvalerate) component of blends. Poly(butylene succinate)/poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/poly(ethylene glycol) ratio of 50:20:30 was chosen owing to its good properties. The poly(3-hydroxybutyrate-co-3-hydroxyvalerate) component of blends can be degraded completely by Pseudomonas mendocina DS04-T, whereas this strain cannot degrade poly(butylene succinate) and poly(ethylene glycol). Apart from poly(butylene succinate), Fusarium sp. FS1301 can also biodegrade poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and poly(ethylene glycol).     

拉伸形变作用下PLA/PBS增韧共混物力学性能研究

通过叶片挤出机对聚乳酸/聚丁二酸丁二醇酯（PLA/PBS）及添加剂进行塑化共混后制备复合增韧体系,研究不同PLA/PBS配比、挤出机转速以及添加剂种类对共混物力学性能的影响。结果表明,随着PBS含量的增加,PLA/PBS共混物的拉伸强度变化不大,而韧性明显提高;当叶片挤出机转速为75 r/min,改性剂邻苯二甲酸二仲辛酯(DCP)含量为0.05 %(质量分数,下同),马来酸酐接枝聚丙烯（PP-g-MAH)含量为1.5 %时,共混物具有最佳力学性能;PLA与PBS相容性较差,但叶片挤出机提供的拉伸力场迫使分散相分散均匀,尺度较小。     

Effect of triphenyl phosphite as a reactive compatibilizer on the properties of poly(L-lactic acid)/poly(butylene succinate) blends

Reactive blending is an innovative method for the improvement of compatibility of polymer blend. In this work, poly ( _L-lactic acid) and poly (butylene succinate) (PLLA/PBS) blends were prepared by melt blending to ameliorate the toughness of PLLA. Triphenyl phosphite (TPP) was introduced into the PLLA/PBS blends (80/20 by weight) to enhance their compatibility via reactive blending. The effects of TPP on the morphology and properties of PLLA/PBS blends were studied systematically. The increased torque during melt blending demonstrated that the compatibilizer successfully reacted with PLLA and PBS. The mechanical properties of the blends were exceedingly improved only with 0.5 wt% TPP. A reduction tendency of size of the dispersed phase was observed due to the improvement of compatibility. The DSC and DMA results indicate that the T _g of PLLA decreased at a slow rate with the increasing content of TPP. This work provided a simple approach for preparing a kind of high toughed PLLA material. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48646.